首页   按字顺浏览 期刊浏览 卷期浏览 Ultrasonic Relaxation and Axial‐Equatorial Isomerization in Methyl Cyclohexane
Ultrasonic Relaxation and Axial‐Equatorial Isomerization in Methyl Cyclohexane

 

作者: J. E. Piercy,  

 

期刊: The Journal of the Acoustical Society of America  (AIP Available online 1961)
卷期: Volume 33, issue 2  

页码: 198-206

 

ISSN:0001-4966

 

年代: 1961

 

DOI:10.1121/1.1908618

 

出版商: Acoustical Society of America

 

数据来源: AIP

 

摘要:

The ultrasonic absorption and velocity of dilute solutions of methyl, chloro‐, and bromocyclohexane in xylene have been measured over the range 0.6 to 25 Mc and 65° to 95°C. The frequency dependence of the absorption in all cases is that of a single relaxation process. The concentration dependence of the relaxation parameters is consistent with the mechanism being the interchange of axial and equatorial chair isomers, while the temperature dependence yields a difference in enthalpy and entropy between isomers of methyl cyclohexane of 3.54±0.7 kcal/mole and 4.04±1.1 cal/mole °C, respectively, and an activation energy for the conversion of axial into equatorial isomers of 10.94±0.8 kcal/mole for methyl cyclohexane and 12±2 kcal/mole for chloro‐ and bromo‐cyclohexane. There is no significant change in these values for methyl cyclohexane when the solvent is changed to nitrobenzene orn‐butyl alcohol, indicating that intermolecular processes do not make an appreciable contribution, and that the difference in volume between isomers can be neglected in the calculations. The conversion of axial into equatorial isomers is found to be uni‐molecular, and a mode of vibration of the molecule similar to either theA1gorEumodes of cyclohexane is suggested for the path of this reaction.

 

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